Editing Formic acid (section)

==Production==
In 2009, the worldwide capacity for producing formic acid was {{convert|720|e3t|e9lb|abbr=off}} per year, roughly equally divided between Europe ({{convert|350|e3t|e6lb|abbr=off|disp=or}}, mainly in Germany) and Asia ({{convert|370|e3t|e6lb|abbr=off|disp=or}}, mainly in China) while production was below {{convert|1|e3t|e6lb|abbr=off|disp=or}} per year in all other continents.<ref name=CEH>{{cite web|url=http://www.sriconsulting.com/CEH/Public/Reports/659.2000/|title=CEH Marketing Research Report: FORMIC ACID|author1=S. N. Bizzari |author2=M. Blagoev |date=June 2010|work=Chemical Economics Handbook|publisher=SRI consulting |archive-url=https://web.archive.org/web/20110914202313/http://www.sriconsulting.com/CEH/Public/Reports/659.2000/ |archive-date=14 September 2011}}</ref> It is commercially available in solutions of various concentrations between 85 and 99 w/w %.<ref name = Ullmann_2009/> {{As of|2009}}, the largest producers are [[BASF]], [[Eastman Chemical Company]], [[LC Industrial]], and [[Feicheng Acid Chemicals]], with the largest production facilities in [[Ludwigshafen]] ({{convert|200|e3t|e6lb|abbr=off|disp=or}} per year, BASF, Germany), [[Oulu]] ({{convert|105|e3t|e6lb|abbr=off|disp=or}}, Eastman, Finland), [[Nakhon Pathom]] (n/a, LC Industrial), and [[Feicheng]] ({{convert|100|e3t|e6lb|abbr=off|disp=or}}, Feicheng, China). 2010 prices ranged from around €650/tonne (equivalent to around $800/tonne) in Western Europe to $1250/tonne in the United States.<ref name=CEH/>

Regenerating CO<sub>2</sub> to make useful products, that displace incumbent fossil fuel based pathways is a more impactful process than CO<sub>2</sub> sequestration.

Both formic acid and CO (carbon monoxide) are C1 (one carbon molecules).  Formic is a hydrogen-rich liquid which can be transported and easily donates its hydrogen to enable a variety of condensation and esterification reactions to make a wide variety of derivative molecules.  CO, while more difficult to transport as a gas, is also one of the primary constituents of syngas useful in synthesizing a wide variety of molecules.  

CO<sub>2</sub> electrolysis is distinct from photosynthesis and offers a promising alternative to accelerate decarbonization. By converting CO<sub>2</sub> into products using clean electricity, we reduce CO<sub>2</sub> emissions in two ways: first and most simply by the amount of CO<sub>2</sub> that is regenerated, but the second way is less obvious but even more consequential by avoiding the CO<sub>2</sub> emissions otherwise generated by making these same products from fossil fuels. This is known as carbon displacement or abatement.

CO<sub>2</sub> electrolysis holds promise for reducing atmospheric CO<sub>2</sub> levels and providing a sustainable method for producing chemicals, materials, and fuels. Its efficiency and scalability are active areas of research, but now also commercialization, aiming to make it a viable commercial technology for both carbon management and molecule production.<ref>{{Cite web |title=Rethinking CO2 in a Circular Economy {{!}} Carbon Capture Magazine |url=https://carboncapturemagazine.com/articles/rethinking-co2-in-a-circular-economy |access-date=2025-03-11 |website=carboncapturemagazine.com}}</ref>

===From methyl formate and formamide===
When [[methanol]] and [[carbon monoxide]] are combined in the presence of a strong [[Base (chemistry)|base]], the result is [[methyl formate]], according to the [[chemical equation]]:<ref name=Ullmann_2009/>
:CH<sub>3</sub>OH + CO → HCO<sub>2</sub>CH<sub>3</sub>

In industry, this reaction is performed in the liquid phase at elevated pressure. Typical reaction conditions are 80&nbsp;°C and 40 atm. The most widely used base is [[sodium methoxide]]. [[Hydrolysis]] of the methyl formate produces formic acid:
:HCO<sub>2</sub>CH<sub>3</sub> + H<sub>2</sub>O → HCOOH + CH<sub>3</sub>OH

Efficient hydrolysis of methyl formate requires a large excess of water. Some routes proceed indirectly by first treating the methyl formate with [[ammonia]] to give [[formamide]], which is then hydrolyzed with [[sulfuric acid]]:
:HCO<sub>2</sub>CH<sub>3</sub> + NH<sub>3</sub> → HC(O)NH<sub>2</sub> + CH<sub>3</sub>OH
:2 HC(O)NH<sub>2</sub> + 2H<sub>2</sub>O + H<sub>2</sub>SO<sub>4</sub> → 2HCO<sub>2</sub>H + (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>

A disadvantage of this approach is the need to dispose of the [[ammonium sulfate]] byproduct. This problem has led some manufacturers to develop energy-efficient methods of separating formic acid from the excess water used in direct hydrolysis. In one of these processes, used by [[BASF]], the formic acid is removed from the water by [[liquid-liquid extraction]] with an organic base.{{citation needed|date=November 2017}}

===Niche and obsolete chemical routes===
====By-product of acetic acid production====
A significant amount of formic acid is produced as a byproduct in the manufacture of other chemicals. At one time, [[acetic acid]] was produced on a large scale by oxidation of [[alkane]]s, by a process that cogenerates significant formic acid.<ref name=Ullmann_2009/> This oxidative route to acetic acid has declined in importance so that the aforementioned dedicated routes to formic acid have become more important.{{cn|date=June 2024}}

====Hydrogenation of carbon dioxide====
The catalytic [[hydrogenation]] of [[Carbon dioxide|CO<sub>2</sub>]] to formic acid has long been studied. This reaction can be conducted homogeneously.<ref>{{Cite book | author = P. G. Jessop | title = Handbook of Homogeneous Hydrogenation | editor = J. G. de Vries, C. J. Elsevier | publisher = Wiley-VCH | location = Weinheim, Germany | date = 2007 | pages = 489–511}}</ref><ref>{{cite journal |doi=10.1016/j.ccr.2004.05.019 |title=Recent advances in the homogeneous hydrogenation of carbon dioxide |journal=Coordination Chemistry Reviews |volume=248 |issue=21–24 |pages=2425 |year=2004 |last1=Jessop |first1=Philip G |last2=Joó |first2=Ferenc |last3=Tai |first3=Chih-Cheng }}</ref><ref>{{Cite web |last=Sampson |first=Joanna |date=2 August 2020 |title=Wireless device makes clean fuel from sunlight, CO2 and water |url=https://www.gasworld.com/wireless-device-makes-clean-fuel-from-sunlight-co2-and-water-/2019694.article |access-date=2020-08-26 |website=Gasworld |language=en}}</ref>

====Oxidation of biomass====
Formic acid can also be obtained by aqueous catalytic partial oxidation of wet biomass by the [[OxFA process]].<ref>{{cite journal |doi=10.1039/C1GC15434F |title=Selective catalytic conversion of biobased carbohydrates to formic acid using molecular oxygen |journal=Green Chemistry |volume=13 |issue=10 |pages=2759 |year=2011 |last1=Wölfel |first1=Rene |last2=Taccardi |first2=Nicola |last3=Bösmann |first3=Andreas |last4=Wasserscheid |first4=Peter |s2cid=97572039 }}</ref><ref>{{cite journal |doi=10.1039/C2EE21428H |title=Selective oxidation of complex, water-insoluble biomass to formic acid using additives as reaction accelerators |journal=Energy & Environmental Science |volume=5 |issue=7 |pages=7956 |year=2012 |last1=Albert |first1=Jakob |last2=Wölfel |first2=Rene |last3=Bösmann |first3=Andreas |last4=Wasserscheid |first4=Peter |bibcode=2012EnEnS...5.7956A |s2cid=93224286 }}</ref> A [[Keggin structure|Keggin-type]] polyoxometalate (H<sub>5</sub>PV<sub>2</sub>Mo<sub>10</sub>O<sub>40</sub>) is used as the homogeneous catalyst to convert sugars, wood, waste paper, or cyanobacteria to formic acid and CO<sub>2</sub> as the sole byproduct. Yields of up to 53% formic acid can be achieved.{{Citation needed|date=November 2018}}

====Laboratory methods====
In the laboratory, formic acid can be obtained by heating [[oxalic acid]] in [[glycerol]] followed by steam distillation.<ref name="chattaway">{{cite journal |doi=10.1039/CT9140500151 |title=XX.—Interaction of glycerol and oxalic acid |journal=[[Journal of the Chemical Society, Transactions]] |volume=105 |pages=151–6 |year=1914 |last1=Chattaway |first1=Frederick Daniel |hdl=2027/mdp.39015067135775 |url=https://zenodo.org/record/2046509 }}</ref> Glycerol acts as a catalyst, as the reaction proceeds through a glyceryl oxalate intermediate. If the reaction mixture is heated to higher temperatures, [[allyl alcohol]] results. The net reaction is thus:
:C<sub>2</sub>O<sub>4</sub>H<sub>2</sub> → HCO<sub>2</sub>H + CO<sub>2</sub><!--esoteric and not useful to anyone: Another preparation is the acid [[hydrolysis]] of ethyl isonitrile (C<sub>2</sub>H<sub>5</sub>NC) using [[hydrochloric acid|HCl]] solution.<ref name="cohen">{{Cite book | author = Cohen, Julius B. | title = Practical Organic Chemistry | publisher = MacMillan | date = 1930}}</ref>
:C<sub>2</sub>H<sub>5</sub>NC + 2 H<sub>2</sub>O → C<sub>2</sub>H<sub>5</sub>NH<sub>2</sub> + HCO<sub>2</sub>H
The isonitrile can be obtained by reacting [[ethyl amine]] with [[chloroform]] (note that the fume hood is required because of the overpoweringly objectionable odor of the [[isonitrile]]).-->
Another illustrative method involves the reaction between [[lead formate]] and [[hydrogen sulfide]], driven by the formation of [[lead sulfide]].<ref>{{Cite book | author = Arthur Sutcliffe | date = 1930 | title = Practical Chemistry for Advanced Students | edition = 1949 | publisher = John Murray | location = London}}</ref>
:Pb(HCOO)<sub>2</sub> + H<sub>2</sub>S → 2HCOOH + PbS

====Electrochemical production====
Formate is formed by the [[electrochemical reduction]] of CO<sub>2</sub> (in the form of [[bicarbonate]]) at a [[lead]] [[cathode]] at pH 8.6:<ref>{{cite journal |display-authors=etal|last1=B. Innocent |title=Electro-reduction of carbon dioxide to formate on lead electrode in aqueous medium |journal=Journal of Applied Electrochemistry |date=Feb 2009 |doi=10.1007/s10800-008-9658-4 |volume=39 |issue=2 |pages=227–232|s2cid=98437382 }}</ref>
:{{chem|HCO|3|-}} + {{chem|H|2|O}} + 2e<sup>−</sup> → {{chem|HCO|2|-}} + 2{{Chem|OH|-}}
or
:{{chem|CO|2}} + {{chem|H|2|O}} + 2e<sup>−</sup> → {{chem|HCO|2|-}} + {{Chem|OH|-}}
If the feed is {{chem|CO|2}} and oxygen is evolved at the anode, the total reaction is:
:{{CO2}} + {{chem|OH|-}} → {{chem|HCO|2|-}} + 1/2 {{O2}}

===Biosynthesis===
Formic acid is named after ants which have high concentrations of the compound in their venom, derived from [[serine]] through a [[5,10-methenyltetrahydrofolate]] intermediate.<ref>{{cite journal|last1=Hefetz|first1=Abraham|last2=Blum|first2=Murray|title=Biosynthesis of formic acid by the poison glands of formicine ants|journal=Biochimica et Biophysica Acta (BBA) - General Subjects|date=1 November 1978|volume=543|issue=4|pages=484–496|doi=10.1016/0304-4165(78)90303-3|pmid=718985}}</ref> The conjugate base of formic acid, formate, also occurs widely in nature. An [[assay]] for formic acid in body fluids, designed for determination of formate after methanol poisoning, is based on the reaction of formate with bacterial [[formate dehydrogenase]].<ref>{{cite journal |doi=10.1016/0006-2944(75)90147-7 |pmid=1 |title=Formate assay in body fluids: Application in methanol poisoning |journal=Biochemical Medicine |volume=13 |issue=2 |pages=117–26 |year=1975 |last1=Makar |first1=A.B |last2=McMartin |first2=K.E |last3=Palese |first3=M |last4=Tephly |first4=T.R }}</ref>